CN109888316A - Nitrogen-doped graphene prepares the method for catalyst, the preparation method of working electrode and its working electrode - Google Patents
Nitrogen-doped graphene prepares the method for catalyst, the preparation method of working electrode and its working electrode Download PDFInfo
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Abstract
The invention discloses a kind of method that nitrogen-doped graphene prepares catalyst, specific steps are as follows: S1, adds graphene oxide into ethylene glycol, H is instilled in graphene oxide2PtCl6Solution is added N-Methyl pyrrolidone solution as nitrogen source, mixed solution is transferred in supersonic wave cleaning machine and carries out ultrasonic disperse, is during which stirred continuously until that graphene oxide powder dissolves；After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution boils, after suspending 10s, continues microwave heating to after boiling, suspend 10s, finally microwave heating 20s, reduction reaction finish again, take out mixed solution and are cooled to room temperature；S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is placed in vacuum drier and is dried, grinding obtains catalyst.Catalytic performance, stability and the anti-poisoning capability of the catalyst of preparation are more excellent than not mixing the graphen catalyst of N.
Description
Technical field
The invention belongs to the sides that catalyst preparation technical field more particularly to a kind of nitrogen-doped graphene prepare catalyst
The preparation method of method, working electrode and its working electrode.
Background technique
Fuel cell assembling is succinct, is easy to use, and wherein the benefit of Direct Ethanol Fuel Cell (DEFC) is more, and ethyl alcohol holds
Easily purchase, environmentally friendly, working efficiency is good, can protect the environment of our existence using it.Although direct alcohol fuel electricity
Pond (DEFC) compared with other kinds of fuel cell, weight, size, in terms of have superiority, however
It is currently also very immature to the research and probe of DEFC, it is also faced during this period to some stubborn problems, your gold such as is being used
When belonging to as catalyst catalytic efficiency it is not high and cause using the amount toxic centre increasing, generated in catalytic reaction process
Product.There is also some shortcomings for current scientific research achievement, generate as ethanol synthesis not exclusively has nuisance, catalyst Pt price
It is expensive and rare, cause the expense of fuel cell to be substantially increased, so that being unfavorable for it reaches industrialization production.
The material overwhelming majority used in DEFC anode catalyst is all by precious metals pt and carbon material both at home and abroad at present
It is composed, wherein in the catalytic process of Pt in the catalyst, to there is some good performances, such as possess lower excessively electric
Position, better catalytic activity, excellent in stability etc..But, although anode catalyst catalytic performance composed by them is good, Pt
It is rare precious metals, its price is high, therefore we should reduce the usage amount of platinum to the greatest extent and improve its catalytic efficiency.Together
When, the intermediate product CO for possessing stronger adsorption capacity can be generated when reaction being catalyzed, and Pt poisoning can be made to reduce it
Activity.So intermediate reaction object CO of the Yao Gaishan generated in catalytic process is to the absorption of Pt electrode and is poisoned
Such case, it is necessary to adulterate other element, it can be acted on rare precious metals Pt generation, is made in catalyst with this
The catalytic process of glassy carbon electrode surface is improved.
Catalyst is exactly supported on carrier by a kind of practical way for improving Direct Ethanol Fuel Cell performance,
In, when loading to Pt, catalyst carrier plays key effect, and carrier also directly affects catalysis using the time
The service life of agent.The microstructure of catalyst carrier and the relevant nature of own, such as its electric conductivity, specific surface area and table
Face functional group etc. all has a certain impact to the interaction tool between catalyst nano-particles and catalyst carrier, this is also influenced
The catalytic performance of the elctro-catalyst of fuel cell.
Wherein, catalytic efficiency is highest remains Pt system metallic catalyst, but during using Pt, still there is one
A little problems such as the problems such as use cost is high, catalytic performance is undesirable, easy poisoning and service life are short, therefore reduce the use of Pt
And the catalytic performance for improving it is particularly significant to popularizing for DEFC, carrying out load to catalyst becomes a kind of feasible pattern.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method that nitrogen-doped graphene prepares catalyst, is preparing
Nitrogen source is introduced in the process, is doped with the catalytic performance of the graphen catalyst of N element, and stability and anti-poisoning capability ratio do not mix N
Graphen catalyst it is more excellent.
In order to solve the above technical problems, the invention provides the following technical scheme:
A kind of method that nitrogen-doped graphene prepares catalyst, specifically includes the following steps:
S1, graphene oxide is prepared first, then the graphene oxide of 140~160mg is added in ethylene glycol, in oxygen
The concentration that 9~11ml is instilled in graphite alkene is 0.039mol/L dissolved with H2PtCl6Ethylene glycol solution, then be added N- first
Mixed solution is transferred in supersonic wave cleaning machine as nitrogen source and carries out ultrasonic disperse, during which persistently stir by base pyrrolidone solution
Until graphene oxide powder dissolves；
The graphene oxide the preparation method comprises the following steps:
1. weighing the concentrated sulfuric acid that 140~160ml concentration is 98%, it is added in the beaker of 500mL, beaker is placed on ice water
In bath, thermometer is shown to 0 DEG C, after stablizing, is first slowly added to 2~4g natural flake graphite powder, is added 4~6g sodium nitrate,
And continuously stirred with machine mixer, when adding sample, guarantees that thermometer is shown and be no more than 6 DEG C, during which if temperature change is big,
It should be waited to be further continued for adding when stablizing to 6 DEG C or less, guarantee that three kinds of material mixings are uniform, and stir 0.5h；
2. slowly potassium permanganate powder is added, adition process it is noted that thermometer temperature display, when temperature is more than 6 DEG C
Stopping being added, the potassium permanganate powder of 17~19g of addition is further continued for after it is reduced, whole process, which is stirred continuously, makes its heat dissipation,
It is completely dissolved in potassium permanganate powder in mixed liquor, during which guarantee system temperature is lower than 6 DEG C, heats up after mixture stirring 90min
To 35 DEG C；
3. continuing to stir 6h by 35 DEG C of reaction system dislocation of thermostat water bath；
4. adding the deionized water of 190~210mL into beaker, water bath with thermostatic control pot temperature is adjusted to 80 DEG C, is further continued for stirring
Mix 2h；
5. 19~21mL of hydrogen peroxide and 120~140mL of deionized water that concentration is 30% are added into beaker stirs 1h, on
Clear liquid is golden yellow；240~260mL of dropwise addition ionized water and 4~6mL concentration are further continued for as 30% hydrogen peroxide, mixture becomes
After buff, 12h is placed；
6. after demixing, outwelling supernatant liquid, yellow suspension is filtered with filter, and filter cake is dense with 19~21mL's
Degree washs for 5% dilute hydrochloric acid, is then washed with deionized water to the pH value of separating liquid and reaches 7；
7. filter cake is placed in crucible, 30 DEG C of dry 10h or more, are then ground to powder, obtain oxygen in a vacuum drying oven
Graphite alkene powder；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, grinding obtains catalyst.
Preferably, in step S1 the mass ratio of N-Methyl pyrrolidone and graphene oxide be 250:1,200:1,150:1,
100:1,50:1 or 25:1.
Preferably, the time of ultrasonic disperse is 40min in step S1.
Preferably, the temperature dry in vacuum drier of step S3 is 20 DEG C, and drying time is 1~2h.
The present invention also provides a kind of working electrodes comprising the method that nitrogen-doped graphene above-mentioned prepares catalyst is made
Catalyst and glass-carbon electrode.
The present invention also provides a kind of preparation methods of working electrode, specifically includes the following steps:
Step 1: the Al of 0.05um is used on chamois leather polishing cloth2O3Glass-carbon electrode is ground to mirror surface by powder, then in ultrasound
In wave three times with deionized water ultrasonic cleaning, EtOH Sonicate cleans three times, and ultrasonic time is 20~40s；
Step 2: preparation 1~3mL mixed solution contains the ethyl alcohol of 20% volume ratio, the water of 73.75% volume ratio,
The Nafion solution of the resinous solid content 5% of 6.25% volume ratio；
Step 3: the catalyst for weighing 3~5mg preparation is added in the mixed solution of 1~3mL step 2 preparation, is made into
New mixed solution handles 30~40min of mixed solution with ultrasonic echography, is uniformly mixed it, then takes out；
Step 4: drawing alcohol washes with micropipettor, draws mixed solution made from 8~10uL step 3 with it and drips
To glass-carbon electrode, then glass-carbon electrode is dried, working electrode is prepared.
Compared with the prior art, the invention has the following advantages:
Catalytic performance, stability and the anti-poisoning capability of catalyst prepared by the present invention are catalyzed than not mixing the graphene of N
Agent is more excellent, and preparation method is simple, the purity is high of obtained catalyst, and C, N, Pt are evenly distributed in catalyst, and Pt receives
Rice corpuscles is uniformly distributed on the surface of graphene.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to do simply to introduce, it should be apparent that, the accompanying drawings in the following description is this hair
Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the flow chart for the method that nitrogen-doped graphene of the invention prepares catalyst；
Fig. 2 is the XRD spectrum of catalyst produced by the present invention；
Fig. 3 a is the SEM figure of catalyst made from embodiment 5；
Fig. 3 b is that the point of catalyst made from embodiment 5 sweeps analysis；
Fig. 4 a is the SEM figure of the catalyst undoped with N；
Fig. 4 b is that the point of the catalyst undoped with N sweeps analysis；
Fig. 5 is seven kinds of catalyst in 0.5mol/L H2SO4H adsorption/desorption curve in solution；
Fig. 6 is seven kinds of catalyst in 1mol/L CH3CH2OH+0.5mol/L H2SO4Cyclic voltammetry curve in solution；
Fig. 7 is seven kinds of catalyst in 1mol/L CH3CH2OH+0.5mol/L H2SO4I-T curve in solution.
Specific embodiment
A specific embodiment of the invention is described in detail with reference to the accompanying drawing, rather than to protection scope of the present invention
Limitation.
The present invention provides a kind of method that nitrogen-doped graphene prepares catalyst, specifically includes the following steps:
S1, graphene oxide is prepared first, then the graphene oxide of 140~160mg is added in ethylene glycol, in oxygen
The concentration that 9~11ml is instilled in graphite alkene is 0.039mol/L dissolved with H2PtCl6Ethylene glycol solution, then be added N- first
Base pyrrolidone solution as nitrogen source, the mass ratio of N-Methyl pyrrolidone and graphene oxide is 250:1,200:1,150:1,
Mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine by 100:1,50:1 or 25:1, and during which persistently stirring is straight
It is dissolved to graphene oxide powder；
Graphene oxide the preparation method comprises the following steps:
1. weighing the concentrated sulfuric acid that 140~160ml concentration is 98%, it is added in the beaker of 500mL, beaker is placed on ice water
In bath, thermometer is shown to 0 DEG C, after stablizing, is first slowly added to 2~4g natural flake graphite powder, is added 4~6g sodium nitrate,
And continuously stirred with machine mixer, when adding sample, guarantees that thermometer is shown and be no more than 6 DEG C, during which if temperature change is big,
It should be waited to be further continued for adding when stablizing to 6 DEG C or less, guarantee that three kinds of material mixings are uniform, and stir 0.5h；
2. slowly potassium permanganate powder is added, adition process it is noted that thermometer temperature display, when temperature is more than 6 DEG C
Stopping being added, the potassium permanganate powder of 17~19g of addition is further continued for after it is reduced, whole process, which is stirred continuously, makes its heat dissipation,
It is completely dissolved in potassium permanganate powder in mixed liquor, during which guarantee system temperature is lower than 6 DEG C, heats up after mixture stirring 90min
To 35 DEG C；
3. continuing to stir 6h by 35 DEG C of reaction system dislocation of thermostat water bath；
4. adding the deionized water of 190~210mL into beaker, water bath with thermostatic control pot temperature is adjusted to 80 DEG C, is further continued for stirring
Mix 2h；
5. 19~21mL of hydrogen peroxide and 120~140mL of deionized water that concentration is 30% are added into beaker stirs 1h, on
Clear liquid is golden yellow；240~260mL of dropwise addition ionized water and 4~6mL concentration are further continued for as 30% hydrogen peroxide, mixture becomes
After buff, 12h is placed；
6. after demixing, outwelling supernatant liquid, yellow suspension is filtered with filter, and filter cake is dense with 19~21mL's
Degree washs for 5% dilute hydrochloric acid, is then washed with deionized water to the pH value of separating liquid and reaches 7；
7. filter cake is placed in crucible, 30 DEG C of dry 10h or more, are then ground to powder, obtain oxygen in a vacuum drying oven
Graphite alkene powder；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst.
Preferably, the present embodiment use graphene oxide the preparation method comprises the following steps:
1. weighing the concentrated sulfuric acid that 150mL concentration is 98%, it is added in the beaker of 500mL, beaker is placed in ice-water bath,
Thermometer is shown to 0 DEG C, after stablizing, is first slowly added to 3g natural flake graphite powder, is added 5g sodium nitrate, and use mechanical stirring
Machine continuously stirs, and when adding sample, guarantees that thermometer is shown and is no more than 6 DEG C, during which if temperature change is big, it should be waited to stablize extremely
It is further continued for adding at 6 DEG C or less, guarantees that three kinds of material mixings are uniform, and stir 0.5h；
2. slowly potassium permanganate powder is added, adition process it is noted that thermometer temperature display, when temperature is more than 6 DEG C
Stop being added, addition 18g is further continued for after it is reduced, whole process is stirred continuously, so that heat is shed well, be stirred continuously simultaneously
Make its heat dissipation, be completely dissolved in potassium permanganate powder in mixed liquor, during which guarantee system temperature is lower than 6 DEG C, mixture stirring
35 DEG C are risen to after 90min；
3. continuing to stir 6h by 35 DEG C of reaction system dislocation of thermostat water bath；
4. adding the deionized water of 200mL into beaker, water bath with thermostatic control pot temperature is adjusted to 80 DEG C, is further continued for stirring 2h；
5. the hydrogen peroxide 20mL and deionized water 130mL that concentration is 30% are added into beaker stirs 1h, supernatant is gold
Yellow；It being further continued for that 250mL ionized water and 5mL concentration is added dropwise to be 30% hydrogen peroxide, after a period of time, mixture becomes buff,
Place 12h；
6. after demixing, outwelling supernatant liquid, yellow suspension is filtered with filter, and filter cake is dilute with the 5% of 20mL
Then salt acid elution is washed with deionized water to the pH value of separating liquid and reaches 7；
7. filter cake is placed in crucible, 30 DEG C of dry 10h or more, are then ground to powder, obtain oxygen in a vacuum drying oven
Graphite alkene powder.
Comparative example:
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), mixed solution is transferred in supersonic wave cleaning machine and is carried out
During which ultrasonic disperse 40min is stirred continuously until that graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 1#.
Embodiment 1
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 3.7mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 2#.
Embodiment 2
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 7.3mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 3#.
Embodiment 3
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 14.7mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 4#.
Embodiment 4
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 22.0mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 5#.
Embodiment 5
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 29.4mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 6#.
Embodiment 6
S1, the graphene oxide of the above-mentioned preparation of 150mg is added in the beaker equipped with 250mL ethylene glycol, then instilled
10mL dissolved with H2PtCl6Ethylene glycol solution (Pt mass 67.788mg), then be added 36.7mL N-Methyl pyrrolidone
(NMP) mixed solution is transferred to progress ultrasonic disperse 40min in supersonic wave cleaning machine, during which persistently stirred by solution as nitrogen source
Until graphene oxide powder dissolves；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution
Boiling after suspending 10s, continues microwave heating to after boiling, suspends 10s, finally microwave heating 20s, reduction reaction finish again, take
Mixed solution is cooled to room temperature out, and covers preservative film；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is set
It is dried in vacuum drier, dry temperature is 20 DEG C, and drying time is 1~2h, and grinding obtains catalyst, number mark
It is denoted as 7#.
Performance test:
(1) XRD characterization of catalyst
X-ray diffraction, by carrying out X-ray irradiation to sample, to its diffraction pattern analysis, it can be seen that sample composition etc. is believed
Breath.Test method is to flatten a small amount of catalyst on organic glass slot, then sample is put into instrument, using Cu target as ray
Source, sweep speed are 3 ° of min-1, scanning angle resolution ratio is 0.05 °, 10 °~90 ° of scanning range, finally soft using Jade6.0
Part analyzes institute's measured data.As shown in Fig. 2, catalyst, that is, 2#~7# the particular peaks prepared using method of the invention
Position is almost the same with standard card 1#'s, using being analyzed using Jade6.0 software it is found that four crystal faces of Pt are respectively
(111), (200), (220), (311), corresponding angle value are 40.01 °, 46.68 °, 68.87 °, 81.73 °.Wherein 23.6 °
Corresponding diffraction maximum is C (002) crystal face.The peak value for removing these appearance occurs, it was demonstrated that prepared without remaining obvious peak
Catalyst be it is pure, without other miscellaneous phases.
(2) SEM and the EDS characterization of catalyst
Scanning electron microscope (JSM-6510) characterizes the microscopic appearance structure of prepared catalyst, is carried with JSM-6510
Energy spectrum analysis (EDS) a little sweep to catalyst, the chemical composition for coming analysis of catalyst surface is swept in face, can learn each in sample
The atomic ratio and mass fraction of element.Observation process is: first conducting resinl being adhered on aluminium foil, then a small amount of catalyst is put down
It is placed on conducting resinl, then fixed sample, and is placed in JSM-6510 type scanning electron microscope, carry out observation analysis catalyst.By
Fig. 3 a it is found that graphene surface there are many folds, be conducive to the attachment of Pt particle.Point in Fig. 3 a is carried out a little sweeping analysis
(as shown in Figure 3b) is it is found that in catalyst, the mass percent that the mass percent of graphene is about 62.26%, N is
The mass percent of 5.32%, Pt are about 32.42%.Wherein, it does not mix in the catalyst (such as Fig. 4 a and 4b) of N, the matter of graphene
Measuring the mass percent that percentage is about 63.78%, Pt is about 36.22%, relatively knows that the catalyst for mixing N reduces the dosage of Pt
It is 11%.Face is carried out to Fig. 3 a and sweeps analysis, it is known that C, N, Pt are evenly distributed in catalyst, and Pt nanoparticle is evenly distributed in stone
The surface of black alkene.
(3) electrochemical active surface of catalyst
Electro-chemical test is to carry out on electrochemical workstation at room temperature, the electrochemical Characterization of catalyst be all
It is carried out in the electrolytic cell of the three-electrode system of standard.Test solution is 0.5molL-1H2SO4Solution.
The size of electrochemical active surface (ESA) is commonly used in being the catalytic activity height for characterizing catalyst, its face
Product size can be calculated with the method for integral, calculation formula:
Electricity when what Q was indicated is H absorption or desorption；
[Pt] represents the lift-launch amount of Pt on electrode, about 30%；
The area of behalf desorption peaks；
V is 0.05v/s；
0.21mC/cm2It is H electricity needed for the absorption of Pt per surface area.
Seven kinds of catalyst are in 0.5mol/L H2SO4H adsorption/desorption curve in solution is as shown in figure 5, with the speed of 50mV/s
Degree is scanned, and range is in -0.3~0.6V.
According to formula (1), by integral calculation, the active surface area of this seven groups of different catalysts has been obtained, as shown in table 1.
The electrochemical active surface of 1 seven kinds of catalyst of table
So the ESA size of seven kinds of elctro-catalysts is 6# > 5# > 4# > 3# > 2# > 7# > 1#.It is found that with N element is not added with
1# is compared, and the 2#~7# catalyst for being added to N element possesses bigger electrochemical active surface, illustrates that N element is being added
Later, the catalytic activity of catalyst is enhanced；When N element being all added in the catalyst, when graphene oxide and NMP mass ratio are
When 1:200, the active surface area of catalyst is maximum, and 56% is increased compared with not mixing N, the reason is that the N suitably than column is added
After element, the dispersion degree of Pt nanoparticle is improved, and reduces its partial size, so that the catalytic activity of Pt is improved, so
The catalytic activity of 6# catalyst is better than other several groups.
(4) the ethyl alcohol cyclic voltammetric characterization of catalyst
Cyclic voltammetry is to study the oxidation and reduction process of electrode in electrochemistry, in the potential range of setting, to survey
Try electrode carry out scan round, by research and analyse curve peak value you can learn that period occur reaction mechanism.Cyclic voltammetric
Test is in 1.0molL-1C2H5OH+0.5mol·L-1H2SO4In solution, test scope: 0.05~1.2V, sweep speed are
50mV/s。
From fig. 6 it can be seen that two peaks in the oxidation process just swept, successively occurs in cyclic voltammetry, all it is
Oxidation peak, ethyl alcohol is oxidized to carbon dioxide when there is first oxidation peak, and ethanol synthesis is acetaldehyde and acetic acid when the second peak, whole
It is a just sweep during, Pt is oxidized entirely.The current density size of first oxidation peak occurred when just sweeping is as alcohol catalysis
The index of oxidation.It is negative sweep during there is a reduction peak, negative when sweeping reduction, the oxide for just sweeping generation is reduced, Pt's
Activity is resumed, and Pt electrode is more pure compared to before, so high, the potential value at peak when negative current peak when sweeping can be than just sweeping
Decline.The oxidation spike potential and current density size of made catalyst are as shown in table 2
The oxidation spike potential and current density of 2 seven kinds of catalyst of table
The size of the peak current density of seven kinds of catalyst is 6# > 5# > 4# > 3# > 2# > 7# > 1#.The peak electricity of 6# catalyst in figure
Current density highest has reached 667.6A/g (Pt) and has improved 68% compared with 1# does not mix the catalyst of N.This is because mixing
Under the N element effect of proper proportion, anode catalyst activity is set to be improved, and then improve the energy to Catalytic oxidation of ethanol
Power.
(5) the I-T curve characterization of catalyst
Fig. 7 is made catalyst in 1.0molL-1C2H5OH+0.5mol·L-1H2SO4I-T curve in solution, test
Solution leads to N230min is handled, to exclude influence of the oxygen to experiment.The native state potential 0.05V of test, test potential 0.6V,
Time is 1100s.
Measure the electrochemical active surface (ESA) that the active important indicator of elctro-catalyst is exactly it.Ordinary circumstance
Under, ESA value is bigger, indicate that the reactivity site of the catalyst is more, that is to say, it is bright it electro-chemical activity it is better.Electrochemistry
Active surface area test: range is -0.3V~-0.6V, sweep speed 50mV/s.Test is in 0.5molL-1H2SO4It is molten
Scan round 10 weeks in liquid guarantee that catalyst sufficiently activates.
Chrono-amperometric is a kind of important method that current density changes over time under the corresponding current potential of measurement, by the polarization tested
The activity and stability of catalyst known to curve.This paper is mainly used for the stability of analysis of catalyst using the means of testing.
Test is in 1.0molL-1C2H5OH+0.5mol·L-1H2SO4It is carried out in solution, the native state potential 0.05V of test, test electricity
Position: 0.6V, setting time 1100s.
As shown in Figure 7, test just start when, the value table of current density is larger, and after 2s made catalyst electric current
Density value starts to reduce, this is because ethyl alcohol in catalytic oxidation process, during which has CO generation, influences the effect effect of catalyst
Fruit, with the growth of time, current density tends towards stability, so current density size when selecting 1000s is urged as electricity is judged
The stability of agent.Steady-state current density when seven kinds of catalysis 1000s is as shown in table 3:
The steady-state current density of 3 seven kinds of catalyst of table
The size of the steady-state current density of made catalyst is followed successively by as 6# > 5# > 4# > 3# > 2# > 7# > 1#.Meanwhile Fig. 7
It can be seen that joined the 2# of N element, 3#, 4#, 5#, 6#, the steady-state current density of 7# catalyst is all than being not added with N element
1# catalyst wants high, illustrates that adding N element can be enhanced the stability of elctro-catalyst, improve the property to Catalytic oxidation of ethanol
Energy.Wherein, 6# catalyst is higher than other several groups to the steady-state current density value of Catalytic oxidation of ethanol, improves compared with 1#
63%, the trend of decaying is also most gentle, so 6# is best to the catalytic oxidation effect of ethyl alcohol, optimal stability, the ability of anti-CO
It is most strong, as a result kissing is tested with cyclic voltammetry and H adsorption/desorption.
To sum up, the catalyst of the electric property of catalyst prepared by the present invention, activity and stability than being not added with N element
Want high.
Meanwhile the present invention also provides a kind of working electrodes comprising nitrogen-doped graphene above-mentioned prepares the side of catalyst
Catalyst made from method and glass-carbon electrode.The preparation method of working electrode specifically includes the following steps:
Step 1: the Al of 0.05um is used on chamois leather polishing cloth2O3Glass-carbon electrode is ground to mirror surface by powder, then in ultrasound
In wave three times with deionized water ultrasonic cleaning, EtOH Sonicate cleans three times, and ultrasonic time is 20~40s；
Step 2: preparation 1~3mL mixed solution contains the ethyl alcohol of 20% volume ratio, the water of 73.75% volume ratio,
The Nafion solution of the resinous solid content 5% of 6.25% volume ratio；
Step 3: the catalyst for weighing 3~5mg preparation is added in the mixed solution of 1~3mL step 2 preparation, is made into
New mixed solution handles 30~40min of mixed solution with ultrasonic echography, is uniformly mixed it, then takes out；
Step 4: drawing alcohol washes with micropipettor, draws mixed solution made from 8~10uL step 3 with it and drips
To glass-carbon electrode, then glass-carbon electrode is dried, working electrode is prepared.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme；Therefore, although this specification is referring to the above embodiments, the present invention has been described in detail, this field
It is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement；And all do not depart from the present invention
Spirit and scope technical solution and its improvement, should all cover within the scope of the claims of the present invention.
Claims (6)
1. a kind of method that nitrogen-doped graphene prepares catalyst, it is characterised in that: itself specifically includes the following steps:
S1, graphene oxide is prepared first, then the graphene oxide of 140~160mg is added in ethylene glycol, in oxidation stone
The concentration that 9~11ml is instilled in black alkene is 0.039mol/L dissolved with H2PtCl6Ethylene glycol solution, then be added N- methyl pyrrole
Mixed solution is transferred in supersonic wave cleaning machine as nitrogen source and carries out ultrasonic disperse, be during which stirred continuously until by pyrrolidone solution
Graphene oxide powder dissolution；
The graphene oxide the preparation method comprises the following steps:
1. weighing the concentrated sulfuric acid that 140~160ml concentration is 98%, it is added in the beaker of 500mL, beaker is placed on ice-water bath
In, thermometer is shown to 0 DEG C, after stablizing, it is first slowly added to 2~4g natural flake graphite powder, adds 4~6g sodium nitrate, and
It is continuously stirred with machine mixer, when adding sample, guarantees that thermometer is shown and be no more than 6 DEG C, during which if temperature change is big, answer
It is further continued for adding when Deng its stabilization to 6 DEG C or less, guarantees that three kinds of material mixings are uniform, and stir 0.5h；
2. slowly potassium permanganate powder is added, adition process it is noted that thermometer temperature display, temperature stops when being more than 6 DEG C
It is added, the potassium permanganate powder of 17~19g of addition is further continued for after it is reduced, whole process, which is stirred continuously, makes its heat dissipation, makes height
Potassium manganate powder is completely dissolved in mixed liquor, and during which guarantee system temperature is lower than 6 DEG C, is warming up to 35 after mixture stirring 90min
℃；
3. continuing to stir 6h by 35 DEG C of reaction system dislocation of thermostat water bath；
4. adding the deionized water of 190~210mL into beaker, water bath with thermostatic control pot temperature is adjusted to 80 DEG C, is further continued for stirring 2h；
5. 19~21mL of hydrogen peroxide and 120~140mL of deionized water that concentration is 30% are added into beaker stirs 1h, supernatant
For golden yellow；240~260mL of dropwise addition ionized water and 4~6mL concentration are further continued for as 30% hydrogen peroxide, mixture becomes deep yellow
After color, 12h is placed；
6. after demixing, outwelling supernatant liquid, yellow suspension is filtered with filter, and filter cake is with the concentration of 19~21mL
5% dilute hydrochloric acid washing, is then washed with deionized water to the pH value of separating liquid and reaches 7；
7. filter cake is placed in crucible, 30 DEG C of dry 10h or more, are then ground to powder in a vacuum drying oven, obtain oxidation stone
Black alkene powder；
After S2, ultrasound, mixed solution is moved into and carries out microwave reduction reaction in micro-wave oven, microwave heating is until mixed solution boils
It rises, after suspending 10s, continues microwave heating to after boiling, suspend 10s, finally microwave heating 20s, reduction reaction finish again, take out
Mixed solution is cooled to room temperature；
S3, the solution magnetic agitation 12h or more for preparing step S2, addition deionized water filter, and obtained filter cake is placed in very
It is dried in empty drying machine, grinding obtains catalyst.
2. the method that nitrogen-doped graphene according to claim 1 prepares catalyst, it is characterised in that: N- first in step S1
The mass ratio of base pyrrolidones and graphene oxide is 250:1,200:1,150:1,100:1,50:1 or 25:1.
3. the method that nitrogen-doped graphene according to claim 1 prepares catalyst, it is characterised in that: ultrasonic in step S1
The time of dispersion is 40min.
4. the method that nitrogen-doped graphene according to claim 1 prepares catalyst, it is characterised in that: step S3 true
Dry temperature is 20 DEG C in empty drying machine, and drying time is 1~2h.
5. a kind of working electrode, it is characterised in that: it includes that any nitrogen-doped graphene preparation of Claims 1 to 4 is urged
Catalyst made from the method for agent and glass-carbon electrode.
6. a kind of preparation method of working electrode, it is characterised in that: itself specifically includes the following steps:
Step 1: the Al of 0.05um is used on chamois leather polishing cloth2O3Glass-carbon electrode is ground to mirror surface by powder, then in ultrasonic wave
Three times with deionized water ultrasonic cleaning, EtOH Sonicate cleans three times, and ultrasonic time is 20~40s；
Step 2: preparation 1~3mL mixed solution contains the ethyl alcohol of 20% volume ratio, the water of 73.75% volume ratio, and 6.25%
The Nafion solution of the resinous solid content 5% of volume ratio；
Step 3: the catalyst for weighing 3~5mg preparation is added in the mixed solution of 1~3mL step 2 preparation, is made into new
Mixed solution handles 30~40min of mixed solution with ultrasonic echography, is uniformly mixed it, then takes out；
Step 4: drawing alcohol washes with micropipettor, and the mixed solution made from its absorption 8~10uL step 3 drops to glass
On carbon electrode, then glass-carbon electrode is dried, working electrode is prepared.
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